Triazine Derivatives

ABSTRACT

Disclosed are triazine derivatives of formula 
     
       
         
         
             
             
         
       
     
     X 1  is a bivalent radical of formula 
     
       
         
         
             
             
         
       
         
         A and A′ independently from each other are unsubstituted or substituted, straight-chain or branched C 1 -C 12 alkylene, which is optionally interrupted by C 5 -C 12 cycloalkylene, N, O or S; C 5 -C 12 cycloalkylene; biphenylene; C 6 -C 10 arylene; or C 5 -C 10 arylene-(C 1 -C 12 alkylene);
 
R 1  is a radical of formula
 
       
    
     
       
         
         
             
             
         
       
     
     R 2  and R 3  independently from each other are hydrogen; C 1 -C 12 alkyl; OR 7 ; NR 7 R 8 ; C 6 -C 10 aryl;
 
X 2  is O, or NH;
 
W 1  is C 1 -C 20 alkyl; or a group Sp-Sil;
     Sp is a straight-chain or branched saturated or single or multiple unsaturated C 3 -C 12  hydrocarbon;
 
Sil is a silane; an oligosiloxane; or a polysiloxane moiety;
 
and
 
R 4 , R 5  R 6 , R 7 , R 8  and R 9  independently from each other are hydrogen; C 1 -C 12 alkyl; or C 3 -C 12 cycloalkyl.

The present invention relates to specific triazine derivatives, preparation of these compounds, the preparation of micronized particles of the new tirazine derivatives and cosmetic compositions comprising these triazine derivatives.

The triazine derivatives correspond to formula

X₁ is a bivalent radical of formula

-   A and A′ independently from each other are unsubstituted or     substituted, straight-chain or branched C₁-C₁₂alkylene, which is     optionally interrupted by C₅-C₁₂cycloalkylene, N, O or S;     C₅-C₁₂cycloalkylene; biphenylene; C₆-C₁₀arylene; or     C₅-C₁₀arylene-(C₁-C₁₂alkylene);     R₁ is a radical of formula

R₂ and R₃ independently from each other are hydrogen; C₁-C₁₂alkyl; OR₇; NR₇R₈; C₆-C₁₀aryl;

X₂ is O, or NH;

W₁ is C₁-C₂₀alkyl; or a group Sp-Sil;

-   Sp is a straight-chain or branched saturated or single or multiple     unsaturated C₃-C₁₂ hydrocarbon;     Sil is a silane; an oligosiloxane; or a polysiloxanes moiety;     and     R₄, R₅R₆, R₇, R₈ and R₉ independently from each other are hydrogen;     C₁-C₁₂alkyl; or C₃-C₁₂cycloalkyl.

C₁-C₁₂alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

C₆-C₁₀aryl is for example naphthyl or preferably phenyl.

C₁-C₁₂alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 2-pentylene 3-pentylene, 2,2′-dimethylpropylene, cyclopentylene, cyclohexylene, n-hexylene, n-octylene, 1,1′,3,3′-tetramethylbutylene, 2-ethylhexylene, nonylene, decylene or dodecylene.

Alkylene may be straight-chain, branched, or, from C₅alkyl upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as O, S, —CO—, N, NH, NR_(x), —OCO—, —CO(OR_(x))—, —CONR_(x)—, —(R_(X))NC(O)—; for example C₁-C₁₀alkylene may be a bivalent radical such as: —CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂—, —CH₂—O—CH₂—, —CH₂CH₂—CH₂CH₂—O—CH₂—CH₂—, —CH₂CH₂—CH(N(CH₃)₂)—CH₂—CH₂—, CH₂—NH₂—CH₂—CH₂, —CH₂CH₂—NH—CH₂CH₂—, —CH₂CH₂—NCH₃—CH₂CH₂—, —CO—CH₂—, —CH₂CO—, —CH₂CH₂—NHCO—CH₂CH₂—, —CH₂CH₂—CONH—CH₃—CH₂CH₂—, —CH₂CH₂—NCH₃CO—CH₂CH₂—, —CH₂CH₂—CONCH₃—CH₃—CH₂CH₂—, —CH₂—NHCO—CH₂CH₂—, —CH₂CH₂—NHCO—CH₂—, —CH₂CH₂—CONH—CH₂— or —CH₂—CONH—CH₂CH₂—. R_(x) is hydrogen or C₁-C₁₂alkyl.

C₅-C₁₀cycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene.

C₆-C₁₀arylene is for example naphthylene like

or preferably phenylene.

Preferred are compounds of formula (1) wherein

R₁ is a radical of formula

R₅ and R₆ independently from each other are hydrogen; or C₁-C₅alkyl; and more preferably, wherein R₅ is C₁-C₅alkyl; or hydrogen; and R₆ is hydrogen.

In formula (1)

X₁ is preferably a radical of formula (1b), wherein A and A′ are C₁-C₄alkylene; or wherein X₁ is preferably a radical of formula (1a), wherein A is C₁-C₅alkylene; or phenylene; and R₉ is hydrogen.

Most preferably in formula (1)

X₁ is selected from

Most preferred are compounds of formula (1), wherein

R₂, R₃ and R₄ are hydrogen.

Preferred are also compounds of formula (1), wherein

Sil is the group SiR₁₀R₁₁R₁₂, wherein

-   R₁₀, R₁₁ and R₁₂ each independently are C₁-C₆alkyl; C₁-C₆alkoxy; or     phenyl; or an oligosiloxane of formula —SiMe_(m)(OSiMe₃)_(n); or an     oligosiloxane of the formulae

wherein Me is methyl; m is 0; 1; or 2; n is 1; 2; or 3; m+n are 3; and u is 0 to 6.

Very most preferred are compounds of formula

R₁ is a radical of formula

X₁ is radical of formula (1a) —NR₉-A-NR₉—; (1c)*-O-A-O-*; and

A, W₁, X₂ and R₉ are defined as in formula (1); and R₅ and R₆ independently from each other are hydrogen; or C₁-C₄alkyl.

Preferred are compounds of formula (2), wherein

R₁ is a radical of formula

X₁ is selected from

R₅ and R₆ independently from each other are hydrogen; or C₁-C₄alkyl.

Examples of compounds of formula (1) are listed in the Table below:

TABLE 1 T

Compound of formula R₁ X₁ (3) —CO(O)—C₂H₅

(4) —CO(O)—C₂H₅ —NH—(CH₂)₂—NH— (5) —CO(O)—C₂H₅

(6) —CO—NH₂

(7) —CO—NH₂ —NH—(CH₂)₂—NH— (8) —CO(O)—C₂H₅

(9)

(10)

(11)

(12)

(13) —CO(O)—CH₃

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28)

(29)

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

(39)

(40)

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55) —CO(O)—CH₃ —NH—(CH₂)₂—NH— (56)

(57)

(58)

(59)

(60)

The compounds of formula (1) are prepared by methods known from the prior art, as disclosed for example in Journal of the Institution of Chemists (inida), 6 (5), p. 197 (1984); or in Journal of the Institution of Chemists (inida), 57 (6), p. 233 (1985); or in EP 818 450. The method generally comprises reacting 2 moles of a halogentriazine of formula (1m), preferably chlorotriazine, with 1 mole of the compound of formula (1n) to give the compound of formula (1) according to the following reaction scheme:

wherein R₁, R₂, R₃, R₄ and X₁ are defined as in formula (1).

The reaction is preferably carried out in dipolar aprotic solvents, like dimethylfomamide, di-methylsulfoxide, sulfolane, N-methyl-pyrrolidone; hydrocarbons like xylene or toluene, tetra-line, petroleum, mesytilene or benzene; hydrogenated halocarbons like chlorobenzene or dichlorobenzene; or without a solvent using an excess of a base like tetraalylamines; or without any solvent and a base in a “melt process”.

The reaction temperature is preferably from 20 to 280, preferably 30 to 200, and most preferably from 40 to 150° C.

Preferred bases used in the present process are trialkylamines like triethylamine, ethyl-iso-propylamine, heterocyclic amines like DABCO or DBU, or inorganic bases like NH₂CO₃ or NaHCO₃.

The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations.

The UV absorbers of formula (1) according to the present invention, depending on the definition of X₁ and R₁ can be used either in the dissolved state (soluble organic filters, solubilized organic filters) or in the micronised state (nanoscalar organic filters, particulate organic filters, UV-absorber pigments).

Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example wet-milling, wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) by reprecipitation from suitable solvents.

The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.

The process for the preparation of the micronized compound of formula (1) is another object of the present invention.

A further object of the present invention is a UV absorber dispersion, comprising

-   (a) a micronised UV absorber of formula (1), each of them having a     particle size from 0.02 to 2 μm, and -   (b) a suitable dispersing agent.

The cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further conventional UV filter.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight and preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes: hydrocarbon oils: silicones or siloxanes, organosubstituted super-fatting agents, surfactants consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as spf enhancers.

Cosmetic or Pharmaceutical Preparations

Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing         preparations in the form of tablet-form or liquid soaps,         soapless detergents or washing pastes,     -   bath preparations, e.g. liquid (foam baths, milks, shower         preparations) or solid bath preparations, e.g. bath cubes and         bath salts;     -   skin-care preparations, e.g. skin emulsions, multi-emulsions or         skin oils;     -   cosmetic personal care preparations, e.g. facial make-up in the         form of day creams or powder creams, face powder (loose or         pressed), rouge or cream make-up, eye-care preparations, e.g.         eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix         creams; lip-care preparations, e.g. lipsticks, lip gloss, lip         contour pencils, nail-care preparations, such as nail varnish,         nail varnish removers, nail hardeners or cuticle removers;     -   foot-care preparations, e.g. foot baths, foot powders, foot         creams or foot balsams, special deodorants and antiperspirants         or callus-removing preparations;     -   light-protective preparations, such as sun milks, lotions,         creams or oils, sunblocks or tropicals, pre-tanning preparations         or after-sun preparations;     -   skin-tanning preparations, e.g. self-tanning creams;     -   depigmenting preparations, e.g. preparations for bleaching the         skin or skin-lightening preparations;     -   insect-repellents, e.g. insect-repellent oils, lotions, sprays         or sticks;     -   deodorants, such as deodorant sprays, pump-action sprays,         deodorant gels, sticks or roll-ons;     -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;     -   preparations for cleansing and caring for blemished skin, e.g.         synthetic detergents (solid or liquid), peeling or scrub         preparations or peeling masks;     -   hair-removal preparations in chemical form (depilation), e.g.         hair-removing powders, liquid hair-removing preparations, cream-         or paste-form hair-removing preparations, hair-removing         preparations in gel form or aerosol foams;     -   shaving preparations, e.g. shaving soap, foaming shaving creams,         non-foaming shaving creams, foams and gels, preshave         preparations for dry shaving, aftershaves or aftershave lotions;     -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de         toilette, eau de parfum, parfum de toilette, perfume), perfume         oils or perfume creams;     -   cosmetic hair-treatment preparations, e.g. hair-washing         preparations in the form of shampoos and conditioners, hair-care         preparations, e.g. pretreatment preparations, hair tonics,         styling creams, styling gels, pomades, hair rinses, treatment         packs, intensive hair treatments, hair-structuring preparations,         e.g. hair-waving preparations for permanent waves (hot wave,         mild wave, cold wave), hair-straightening preparations, liquid         hair-setting preparations, hair foams, hairsprays, bleaching         preparations, e.g. hydrogen peroxide solutions, lightening         shampoos, bleaching creams, bleaching powders, bleaching pastes         or oils, temporary, semi-permanent or permanent hair colourants,         preparations containing self-oxidising dyes, or natural hair         colourants, such as henna or camomile.

Presentation Forms

The final formulations listed may exist in a wide variety of presentation forms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W         or PIT emulsion and all kinds of microemulsions,     -   in the form of a gel,     -   in the form of an oil, a cream, milk or lotion,     -   in the form of a powder, a lacquer, a tablet or make-up,     -   in the form of a stick,     -   in the form of a spray (spray with propellent gas or pump-action         spray) or an aerosol,     -   in the form of a foam, or     -   in the form of a paste.

Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.

Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.

A. PREPARATION EXAMPLES Example A1 Preparation of the Compound of Formula

1.8 g (0.021 mol) piperazine are added to a solution of 4.4 g (0.01 mol) of the monochlorotriazine of formula

in 50 ml dimethylformamide and stirred at 75° C. for 2 h.

The reaction solution is decanted on 100 ml water and stirred.

The raw product is filtered off, washed with water, stirred in aceton, filtered off and dried in vacuo at 80° C.

A white product is obtained.

Yield: 2.0 g (44.6%) colorless crystals; Fp=287-290° C.

NMR:

¹³C NMR (90 MHz): δ=14.61 (CH₃), 60.63. (CH₂), 119.35 (CH), 122.99 (Cq), 130.35 (CH), 145.02 (Cq), 164.38 (Cq), 164.98 (Cq), 165.88 (Cq).

Example A2 Preparation of the Compound of Formula

0.3 g ethylendiamine (0.005 mol) and 1.1 g triethylamine (0.011 mol) are added to a solution of 4.4 g (0.01 mol) of the monochlorotriazine of formula (101a) in 50 ml dimethylformamide and stirred for 2 h at 75° C.

The reaction solution concentrated with a rotary evaporator until drying, gathered in water and weakly acidified with hydrochloric acid (1N).

The raw product is filtered off and washed neutral.

After decocting in acetone a white product is obtained.

Yield: 2.7 g (62.0%); Fp=213-215° C.

¹³C NMR (90 MHz): δ=14.55 (CH₃), 14.58 (CH₃), 60.52 (CH₂), 60.55 (CH₂), 119.20 (CH), 122.73 (CH), 122.82 (CH), 130.15 (CH), 145.13 (Cq), 145.29 (Cq), 164.22 (Cq), 164.41 (Cq), 165.87 (Cq), 166.16 (Cq).

Example A3 Preparation of the Compound of Formula

A solution of 34.7 g (0.255 mol) 4-aminobenzamide in 100 ml methyl-2-pyrrolidone is added to a solution of 46.1 g cyanuric chloride (0.25 mol) in a 800 ml dioxan/water mixture (9:1) at 5° C. and a pH of 3.5.

Then a solution of 34.7 g 4-aminobenzamide (0.255 mol) in 100 ml methylpyrrolidone is added at 60-90° C. and pH of 8.5.

The suspension is diluted at 60° C., filtered off warm and washed with dioxan and water.

After decocting with in dimethylfomamide and acetone a white product of formula

is obtained.

0.432 g (0.005 mol) piperazine and 1.1 g triethylamine (0.01 mol) are added to a solution of 3.84 g (0.01 mol) of the monochlorotriazine of formula (103a) in dimethylfomamide.

The reaction mixture is stirred at 75° C. for 6 h and then at 90° C. for 1 h.

After concentrating with the rotary evaporator until drying the residue is gathered in water, weakly acidified with hydrochloric acid, filtered off and washed neutral with water.

After recrystallization from 1-methyl-2-pyrrolidone and decocting in methanol a white product is obtained.

Yield: 1.95 g (49.9%)

Melting point: decomposition starting at 260° C.

Elemental analysis of the compound of formula (103:

C H N Calculated 58.45 4.65 28.70 Found 58.07 4.93 28.13

Example A4 Preparation of the Compound of Formula

0.30 g (0.005 mol) ethylenediamine and 1.1 g triethylamine (0.01 mol) are added to a solution of 3.84 g (0.01 mol) of the monochlorotriazine of formula (103a) in 50 ml dimethylformamide and stirred for 5.5 h at 75° C.

The clear solution is concentrated with a rotary evaporator until drying, gathered in water, weakly acidified with hydrochloric acid, filtered off and washed neutral with water.

After recrystallization from a dimethylformamide/water mixture (4:6) and decocting in acetone a white product is obtained.

Yield: 0.8 g (21.2%)

NMR:

¹³C NMR (90 MHz): δ=31.14, 36.14, 119.26 (CH), 127.72 (Cq), 128.51 (CH), 128.69, 143.09 (Cq), 162.70 (Cq), 163.35 (CH), 163.90 (Cq), 165.13 (Cq), 168.03 (Cq).

Example A5 Preparation of the Compound of Formula

0.37 g (0.005 mol) propylenediamine and 1.1 g (0.01 mol) triethylamine are added to a solution of 4.4 g (0.01 mol) of the monochlorotriazine of formula (101a) in 50 ml dimethylformamide and stirred for 4 h at 75° C.

After concentrating with the rotary evaporator until drying the residue is gathered in water and filtered off.

After dissolving in tert. butylmethylether the organic phase is shaken out with brine solution (5%), dried over sodium sulfate and concentrated until drying.

A white product is obtained by column chromatographic purification.

Yield: 2.3 g (52%)

NMR:

¹³C NMR (90 MHz): δ=14.53 (CH₃), 14.58 (CH₃), 19.04 (CH₃), 46.03. (CH₂), 46.68. (CH), 60.54 (CH₂), 119.22 (CH), 122.73 (Cq), 122.85 (Cq), 130.13 (CH), 145.11 (Cq), 145.25 (Cq), 145.32 (Cq), 164.25 (Cq), 164.38 (Cq), 165.75 (Cq), 165.84 (Cq), 165.87 (Cq), 166.26 (Cq).

Example A6

The compound of formula (5) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by p-phenylene-diamine.

Example A7

The compound of formula (18) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine (CAS No. 2855-13-2). The compound of formula (101a) is replaced by

Example A8

The compound of formula (19) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4′-diamino-3,3′-dimethyldicyclohexylmethane. The compound of formula (101a) is replaced by

Example A9

The compound of formula (20) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-1,12-diamine. The compound of formula (101a) is replaced by

Example A10

The compound of formula (30) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by isophoron-diamine. The compound of formula (101a) is replaced by

Example A11

The compound of formula (32) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by dodecane-1,12-diamine. The compound of formula (101a) is replaced by

Example A12

The compound of formula (43) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4′-diamino-3,3′-dimethyldicyclohexylmethane The compound of formula (101a) is replaced by

Example A13

The compound of formula (31) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 4,4′-Diamino-3,3′-dimethyldicyclohexylmethane. The compound of formula (101a) is replaced by

Example A14

The compound of formula (51) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (101a) is replaced by

Example A15

The compound of formula (53) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by neopentylglycol (CAS No. 126-30-7). The compound of formula (101a) is replaced by

Example A16

The compound of formula (57) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by neopentylglycol. The compound of formula (101a) is replaced by

Example A17

The compound of formula (50) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (101a) is replaced by

Example A18

The compound of formula (49) (Table 1) is prepared according to the method as described in Example 1. Piperazine is replaced by 1,6-hexandiol. The compound of formula (101a) is replaced by

B. APPLICATION EXAMPLES

A % B % C % D % E % F % G % INCI-Name w/w w/w w/w w/w w/w w/w w/w Example B1: Ethylhexyl Methoxycinnnamate 9.8 9.8 9.8 9.8 9.8 9.8 9.8 Cyclomethicone 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefin/isopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer Cyclopentasiloxane (and) 7.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Isododecane (and) 8.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer Ethylhexyl Palmitate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Pentaerythrityl Distearate 1.5 3.0 Glyceryl Dibehenate (and) Tribehenin (and) 2.0 4.0 Glyceryl Behenate Glyceryl Stearate 1.5 1.5 1.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 2.5 Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 6.0 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 5.0 Triglycerides Potassium Cetyl Phosphate 1.8 1.8 VP/Eicosene Copolymer 0.6 0.6 Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Methylene Bis-Benzotriazolyl 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Tetramethylbutylphenol PVP/dimethylconylacrylate/polycarbamyl/polyglycol ester Polyester-5 Acrylates/Palmeth-25 Acrylate Copolymer 0.3 Disteareth-75 IPDI 0.3 3.0 Disteareth-100 IPDI 0.3 3.0 Acrylates/Vinyl Neodecanoate Crosspolymer 1.5 5.0 Compound of formula (56) or (3) or (12) or (17) or 2.0 4.0 6.0 8.0 10.0 12.0 14.0 (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS 5.0 9.0 3.0 1.0 7.0 2.0 15.0 No. 31274-51-8] Glycerin 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Phenoxyethanol (and) Methylparaben (and) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Example B2 C12-15 Alkyl Benzoate 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Butyl Methoxydibenzoylmethane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Octocrylene 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Isohexadecane 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Cyclopentasiloxane 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Terephthalylidene Dicamphor Sulfonic Acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Titanium Dioxide particles size 10 to 100 nm 1.7 1.7 1.7 1.7 1.7 1.7 1.7 TiO2 (and) isodeceth-6(and)Oleth- 1.5 1.0 10(and)Alumina(and) Simethicone Alumina coated TiO2 2.0 4.0 TiO2(and)isolaureth-4 Phosphate(and)Vinylbuteth- 0.5 0.5 0.5 0.5 0.5 0.5 0.5 25/Sodium maleate copolymer TiO2(and)Diethylhexylcarbonate(and)polyglyceryl- 0.8 0.8 0.8 0.8 0.8 0.8 0.8 6 polyhydroxystearate TiO2(and)Aluminum hydroxide(and)Dimethiconol 3.0 methicone copolymer TiO2(and)Aluminum hydroxide(and)Dimethiconol 2.0 methicone copolymer Silica coated TiO2 3.0 TiO2(and)Aluminium hydroxide(and) Isostearic 7.0 acid Maganese modified TiO2 8.0 ZnO particles size 10 to 100 nm 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 1.5 1.0 Glyceryl Dibehenate (and) Tribehenin (and) 2.0 4.0 Glyceryl Behenate Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PEG-100 Stearate (and) Glyceryl Stearate 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefin/isopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer Cyclopentasiloxane (and) 7.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Isododecane (and) 8.0 Acrylates/Polytrimethylsiloxymethacrylate Copolymer Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer C20-22 Alkyl Phosphate (and) C20-22 Alcohols 2.5 3.0 Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 5.0 6.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 4.0 Triglycerides Potassium Cetyl Phosphate 1.3 1.3 PVP/Eicosene Copolymer 1.0 Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Glycerin 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Compound of formula (56) or (3) or (12) or (17) or 2.0 4.0 6.0 8.0 10.0 12.0 14.0 (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) Micronized 2,4,6-Tris(p-biphenylyl)-s-triazine [CAS 5.0 9.0 3.0 1.0 7.0 2.0 15.0 No. 31274-51-8] Propylene Glycol 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Xanthan Gum 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PVP/dimethylconylacrylate/polycarbamyl/polyglycol ester Polyester-5 Disteareth-75 IPDI 0.3 3.0 Disteareth-100 IPDI 0.3 3.0 Acrylates/Vinyl Neodecanoate Crosspolymer 1.5 5.0 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.2 Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Triethanolamine Qs Qs Qs Qs Qs Qs Qs Dimethicone 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Phenoxyethanol (and) Methylparaben (and) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Example B3 Synthetic Beeswax 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate (stabilized by 9.8 9.8 9.8 9.8 9.8 9.8 9.8 incorporating into a polymer) Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane (stabilized by 4.0 4.0 5.0 4.0 4.0 4.0 3.0 incorporating into a polymer) 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 3.0 2.0 1.0 1.0 1.0 1.0 Octadecene/MA Copolymer (and) Methyl Acethyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38 olefin/isopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0 Copolymer Cyclopentasiloxane (and) Acrylates/Polytrimethyl- 7.0 siloxymethacrylate Copolymer Isododecane (and) Acrylates/Polytrimethylsiloxy- 8.0 methacrylate Copolymer Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone Copolymer Dimethicone 4.5 4.5 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0 3.0 Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 4.0 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 1.5 3.0 Glyceryl Dibehenate (and) Tribehenin (and) 2.0 4.0 Glyceryl Behenate Hydroxypropyl Dimethicone Behenate 2.2 1.0 2.2 2.2 0.5 Decyl Cocoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Compound of formula (56) or (3) or (12) or (17) or 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) 1,1′-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)- 2.0 3.0 1.0 8.0 4.0 3.0 1.0 2-hydroxybenzoyl]phenyl]-methanone (CAS No. 919803-06-8) Decyl Glucoside 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate/VP Copolymer 0.3 0.3 0.3 0.3 0.3 0.3 0.3 PVP/dimethylconylacrylate/polycarbamyl/polyglycol ester Polyester-5 Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Disteareth-75 IPDI 0.3 3.0 Disteareth-100 IPDI 0.3 3.0 Acrylates/Vinyl Neodecanoate Crosspolymer 1.5 5.0 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.2 Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Methylene Bis-Benzotriazolyl 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Tetramethylbutylphenol Tromethamine 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and) Cyclopentasiloxane 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Phenoxyethanol (and) Methylparaben (and) Ethyl- 0.8 0.8 0.8 0.8 0.8 0.8 0.8 paraben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone 2.0 1.5 2.0 1.0 (Octyl triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene 3.0 4.0 5.0 1.0 5.0 CAS-Regno. 180898-37-7, Disodium 3.0 4.0 5.0 3.0 phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan APC CAS-Regno. 302776-68-7, Uvinul A Plus 4.0 5.0 CAS-Regno. 444811-29-4, Propanedioic acid, [(4- 3.0 1.0 hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2- ethylhexyl) ester (Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.0 2-phenylethylbenzoate 1.0 1.0 CAS-Regno. 68890-66-4, Octopirox 2.0 3.0 1.0 Tinogard TT (INCI Tetradibutyl Pentaerithrityl 1.0 1.0 1.0 3.0 Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0 3.0 3.0 Butylphenol Sulfonate) Tinogard TL (INCI Benzotriazolyl Dodecyl p- 2.0 1.0 1.0 1.0 3.0 Cresol) Phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4- 2.0 3.0 methyl-, branched and linear Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.0 Butylphenol Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 2.0 1.0 Tris(tetramethylhydroxypiperidinol) citrate 1.0 1.0 (Tinogard Q) 220410-74-2 4-Piperidinol, 1-hydroxy-2,2,6,6- 1.0 1.0 tetramethyl-, 2-hydroxy-1,2,3- propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea 5.0 10.0 CAS-Regno. 2078-71-9, N-(2-Hydroxyethyl)urea 10.0 10.0 mixture of n-butylphthalimide and 0.5 5.0 isopropylphthalimide CAS-Regno. 872424-70-9 2.0 1.0 CAS-Regno. 872424-71-0 2.0 1.0 CAS-Regno. 872424-72-1 2.0 1.0 CAS-Regno. 872424-73-2 2.0 mixture of glycosylglycerides or 2-O-beta- 3.0 2.0 glucopyranosyl-sn-glycerin diaminobenzimidazole 0.1 dihydroxyacetone 2.0 4.0 2.0 2.0 carnitine 3.0 1.0 1.0 Tropolone 0.3 0.2 CAS-Regno. 130603-71-3, alpha-Glucosylrutin 0.5 0.1 1.0 CAS-Regno. 425371-14-8 CAS-Regno. 425371-15-9 CAS-Regno. 261356-13-2 2.0 CAS-Regno. 425371-03-5 2.0 CAS-Regno. 425371-04-6 2.0 CAS-Regno. 25371-05-7 2.0 CAS-Regno. 425371-06-8 2.0 CAS-Regno. 425371-07-9 2.0 CAS-Regno. 425371-08-0 CAS-Regno. 425371-09-1 CAS-Regno. 425371-10-4 CAS-Regno. 425371-11-5 2.0 CAS-Regno. 494198-67-3 CAS-Regno. 803699-05-0 CAS-Regno. 803699-07-2 2.0 CAS-Regno. 803699-09-4 2.0 CAS-Regno. 803699-11-8 2.0 CAS-Regno. 803699-14-1 2.0 CAS-Regno. 803699-15-2 2.0 CAS-Regno. 803699-17-4 2.0 CAS-Regno. 803699-18-5 CAS-Regno. 88137-31-9 3.0 CAS-Regno. 101220-33-1 2.0 CAS-Regno. 875878-17-4 CAS-Regno. 875878-18-5 CAS-Regno. 916463-32-6 2.0 CAS-Regno. 880761-99-9 2.0 CAS-Regno. 880761-95-5 2.0 Example B4 C12-15 Alkyl Benzoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Butyl Methoxydibenzoylmethane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Octocrylene 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Neopentyl Glycol Diheptanoate 6.0 5.0 Propylene Glycol Dibenzoate 4.0 Polyester-7 and Neopenthyl Glycol 8.0 Diheptanoate Diethylhexyl Syringylidenemalonate 6.0 Polyester 8 4.0 Diethylhexyl Malate 7.0 PPG-3 Myristyl Ether Neoheptanoate 6.0 Phenethyl Benzoate 8.0 Isopropyl PPG-2 Isodeceth-7 Carboxylate Isopropyl C12-15-Pareth-9 Carboxylate Cetyl PPG-2 Isodeceth-7 Carboxylate Isohexadecane 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Cyclopentasiloxane 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Terephthalylidene Dicamphor Sulfonic 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Acid Titanium Dioxide particles size 10 to 1.7 1.7 1.7 1.7 1.7 1.7 1.7 100 nm Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 PEG-100 Stearate (and) Glyceryl 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Stearate Potassium Cetyl Phosphate 1.3 1.3 1.3 1.3 1.3 1.3 1.3 PVP/Eicosene Copolymer 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Glycerin 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Compound of formula (56) or (3) or (12) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 or (17) or (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) 1,1′-(1,4-piperazinediyl)bis[1-[2-[4- 2.0 4.0 3.0 4.0 2.0 1.0 4.0 (diethylamino)-2- hydroxybenzoyl]phenyl]-methanone (CAS No. 919803-06-8) Micronized 2,4,6-Tris(p-biphenylyl)-s- 5.0 9.0 3.0 1.0 7.0 2.0 15.0 triazine [CAS No. 31274-51-8] Propylene Glycol 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Xanthan Gum 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Acrylates/C10-30 Alkyl Acrylate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Crosspolymer Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Triethanolamine Qs Qs Qs Qs Qs Qs Qs Dimethicone 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Phenoxyethanol (and) Methylparaben 0.7 0.7 0.7 0.7 0.7 0.7 0.7 (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Example B5 Synthetic Beeswax 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 9.8 9.8 9.8 Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane 2.8 2.8 2.8 2.8 2.8 2.8 2.8 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Methoxyphenyl Triazine Dimethicone 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Cetearyl Alcohol (and) Dicetyl Phos- 4.5 4.5 4.5 4.5 4.5 4.5 4.5 phate (and) Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Butylene Glycol Cocoate 4.0 6.0 4.0 3.0 2.0 1.0 2.5 Hydroxypropyl Dimethicone 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Behenate Decyl Cocoate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Aqua Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Qs to 100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Micronized 2,4,6-Tris(p-biphenylyl)-s- 1.0 3.0 2.0 2.0 1.0 0.5 1.0 triazine [CAS No. 31274-51-8] Micronized 1,1′-(1,4-piperazinediyl)- 3.0 1.0 1.0 4.0 2.0 1.0 3.0 bis[1-[2-[4-(diethylamino)-2-hydroxy- benzoyl]phenyl]-methanone (CAS No. 919803-06-8) Compound of formula (56) or (3) or 4.0 3.0 2.0 1.0 3.0 5.0 3.0 (12) or (17) or (18) or (19) or (20) or (24) or (30) or (31) or (32) or (35) or (41) or (42) or (43) or (44) or (50) or (51) or (53) Octocrylene 2.0 4.0 6.0 8.0 10.0 10.0 8.0 Decyl Glucoside 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ammonium Acryloyldimethyltaurate/- 0.3 0.3 0.3 0.3 0.3 0.3 0.3 VP Copolymer Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Acrylates/C10-30 Alkyl Acrylate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Crosspolymer Disodium EDTA 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Methylene Bis-Benzotriazolyl Tetra- 5.0 5.0 5.0 5.0 5.0 5.0 5.0 methylbutylphenol Tromethamine 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Styrene/Acrylates Copolymer 5.0 3.0 PEG-6 Isostearate (and) Hesperetin 3.0 1.0 4.0 Laurate Polyacrylate-15 (and) Polyacrylate-17 4.0 Carthamus Tinctorius (Safflower) 5.0 Oleosomes PTFE 4.0 Cyclohexasiloxane (and) Cyclopenta- 0.8 0.8 0.8 0.8 0.8 0.8 0.8 siloxane Phenoxyethanol (and) Methylparaben 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (and) Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 

1. Compounds of formula (1)

wherein X₁ is a bivalent radical of formula

A and A′ independently from each other are unsubstituted or substituted, straight-chain or branched C₁-C₁₂alkylene, which is optionally interrupted by C₅-C₁₂cycloalkylene, N, O or S; C₅-C₁₂cycloalkylene; biphenylene; C₆-C₁₀arylene; or C₅-C₁₀arylene-(C₁-C₁₂alkylene); R₁ is a radical of formula

R₂ and R₃ independently from each other are hydrogen; C₁-C₁₂alkyl; OR₇; NR₇R₈; or C₆-C₁₀aryl; X₂ is O, or NH; W₁ is C₁-C₂₀alkyl; or a group Sp-Sil; Sp is a straight-chain or branched saturated or single or multiple unsaturated C₃-C₁₂ hydrocarbon; Sil is a silane; an oligosiloxane; or a polysiloxane moiety; and R₄, R₅, R₆, R₇, R₈ and R₉ independently from each other are hydrogen; C₁-C₁₂alkyl; or C₃-C₁₂cycloalkyl.
 2. Compounds according to claim 1 wherein R₁ is a radical of formula

R₅ and R₆ independently from each other are hydrogen; or C₁-C₅alkyl.
 3. Compounds according to claim 2, wherein R₅ is C₁-C₅alkyl; or hydrogen; and R₆ is hydrogen.
 4. Compounds according to claim 1, wherein X₁ is a radical of formula (1b), wherein A₁ and A₂ are C₁-C₄alkylene.
 5. Compounds according to claim 1, wherein X₁ is a radical of formula (1a), wherein A₁ is C₁-C₅alkylene; or phenylene; and R₉ is hydrogen;
 6. Compounds according to claim 1, wherein X₁ is selected from


7. Compounds according to claim 1, wherein R₂, R₃ and R₄ are hydrogen.
 8. Compounds according to claim 1, wherein Sil is the group SiR₁₀R₁₁R₁₂, wherein R₁₀, R₁₁ and R₁₂ each independently are C₁-C₆alkyl; C₁-C₆alkoxy; or phenyl; or an oligosiloxane of formula —SiMe_(m)(OSiMe₃)_(n); or an oligosiloxane of the formulae

wherein Me is methyl; m is 0; 1; or 2; n is 1; 2; or 3; m+n are 3; and u is 0 to
 6. 9. Compounds according to claim 1, which conform to formula (2)

wherein R₁ is a radical of formula

X₁ is radical of formula

and R₅ and R₆ independently from each other are hydrogen; or C₁-C₄alkyl.
 10. Compounds according to claim 9, wherein R₁ is a radical of formula

X₁ is selected from

 and R₅ and R₆ independently from each other are hydrogen; or C₁-C₄alkyl.
 11. Process for the preparation of compounds of formula (1) according to claim 1, which process comprises reacting 2 moles of a chlorotriazine of formula (1m) with 1 mole of a compound of formula (1n) according to the following reaction scheme:


12. Process for the preparation of a micronized compound of formula (1) according to claim 1, comprising wet-milling, wet-kneading, spray-drying from a suitable solvent, by expansion according to the RESS process or by reprecipitation from suitable solvents of a compound of formula (1) to obtain microparticles having a mean particle size from 0.020 to 2 μm.
 13. Cosmetic composition comprising at least one compound of formula (1) according to claim 1 together with cosmetically tolerable carriers or adjuvants.
 14. Cosmetic composition according to claim 13 wherein the compound of formula (1) is present in the composition in the micronized state.
 15. UV absorber dispersion, comprising (a) at least one micronised UV absorber of formula (1) according to claim 1, having a particle size from 0.02 to 2 μm, and (b) a suitable dispersing agent. 